Polytrifluorochloroethylene and barium peroxide



U ted States Paten POLYTRIFIJUOROCHLQRGETHYLENE AND BARIUM PERUXIDE William ErHanford, Short Hills, N; J assignor, by mesne assignments, to Minnesota Mining and Manufacturing Company, St. Paul, Minn., a corporation of Delaware No Drawing. Application April 20, 1955 Serial N0. 502,718

8 Claims. .(Cl- 260-455) This invention relates to the treatment of perfiuorochloroolefin polymers. In one aspect, the invention relates to the stabilization ofpolymers of trifluorochloroethylene. In another aspect, the invention relates 'to a method of improving heat aging characteristics of ,polytrifluorochloroethylene plastics;

Polymers of trifiuorochloroethylene are prepared :by the polymerization of the monomer, trifluorochloroethylene. The preparation of monomeric trifluorochloroethylene may be accomplished by various methods. One method comprises dechlorinating trifluorotrichloroethane, commercially available as Freon 113, under suitable conditions of dechlorination in the presence of a suitable solvent, such as methyl alcohol, with a dehalogenating agent, such as ZlIlCLdllCt, to product an eiiiuentcomprising the monomer, unreacted' trifiuorotrichloroethane and solvent. Another method comprises dechlorinating trifluorotrichloroethane by passing said material over a catalyst selected from the group 113 and group VIII metals, and combinations thereof, in the presence of hydrogen, at a temperature above about 200 C. The efiluent obtained from either of the above outlined processes is then passed to a suitable fractional distillation system in which substantially pure trifluorochloroethylene is recovered. 'Itis'usually preferred to conduct distillations the presence of a terpene compound. at a temperature above about 25 Cfsince this treatment removes impurities which are detrimental to the production of high, molecular weight polymers. The terpene treatmentstep may be conducted with the first distillation step or atany convenient time prior to the introduction of the monomer into the polymerization zone.

'.The .monomer, obtained as described above, is poly merized. under suitable polymerization conditions with or without'the presence of a suitable catalyst-or promoter. such conditions may comprise the useof a suitable catalyst, such as bis-trichloroacetyl peroxide, dissolved in a suitable solvent suchas trichlorofiuoromethane at a temperaturei'between about 20 C. and about 50 C. An additional polymerization process employing substantially the same conditions asdescribed above may be used. Inthisprocess, adiiierent type of polymerization reactoris employed andthe polymer is formed as a suspension in the monomer and is recovered therefrom-by evaporation.

The polymerproducedabyueitherof the above described processes .is characterized .by wholly difierent chemical and physical characteristics than otherwise similar but non-fluorinated polymeric materials. The chemical resistance of polymers of trifluorochloroethylene is such that they will -withstaud. exposure to a Wide variety of oxidizing, reducing and .solventetyp'e material such as turning nitric 'acid,.co'ncentrated sulfuric acid, hydrazine, hydrogen peroxide, acetone, aniline, etc. Physically, the thennoplasticimaterial possesses high heat stability, tensile strength, .etc; In 'addition tothe above, the thermoplastic peratures so closely approach the degradation tempera- I ture that under ordinary conditions it is extremely difficult to mold the polymer without some degradation, however slight.

,It is an object of this invention to provide-a process for improving the thermal stability of perfiuorochloroolefin polymers.

It is another object of this invention to provide a means for stabilizing polymers of trifluorochloroethylene.

'It is one of the more particular objects of this invention to improve the thermal stability of polymers of trifiuorochloroethylene.

It is another of the particular objects of this invention to provide a means for molding polymers of triiiuorochloroethylene at temperatures approaching decomposition temperature.

polymersare readily molded into' various useful articles Various other objects and advantages of the present invention will become apparent to those skilled in the art on reading the accompanying description and disclosure.

Generally, the above objects are accomplished by admixing with, and intimately dispersing within the polymer a'minor proportion of barium peroxide which functions as a stabilizing agent and which improves the thermal stability of perfluorochloroolefin polymers and particularly polymers of trifiuorochloroethylene.

Stabilization of the polymer is eiiected by admixing with, and intimately dispersing within the polymer between about 0.05 and about 20 parts of barium peroxide per parts of polymer by weight, and preferably between about 0.1 and about 10 parts of barium peroxide per 100 of the polymer. The exact concentration of the stabilizing agent employed will be determined by the use for which the polymer is intended. Thus, when the polymer is to be used as a molding powder, it is preferred to use between about 0.1 and about 3 parts of the stabilizing agent per' 100 parts of polymerg'whereas when used in the form of a dispersion, for example, in Xylene, di-isobutyl ketone, amyl acetate, water, acetone, etc., it is preferred to use between about 3 and about 7 parts of barium peroxide per 100 parts of polymer.

The polymers which are particularly suited to the process of this invention are the high molecular weight, normally solid thermoplastic polymers. Since the determination of molecular weight of the perfluorochloroolefin polymers, such as polytrifluorochloroethylene, is tedious and expensive, it has become an accepted practice to express the molecular weight of the polymer in terms of its ZST value which is dependent on the molecular weight. Thus, homopolymers of trifiuorochloroethyl ene which are particularly suited to the process of this invention have a ZST'value of above about 125.

This invention also contemplates the treatment of copolymers of trifiuorochloroethylene containing below about 70 mol percent of fluorine containing olefins, such as perfluorobutadiene, vinylidene fluoride, difluorodichloroethylene, diiluoroethylene, trifluoroethylene, periluorosty'- rene, perfiuorocyclobutene, and phenyltrifluoroethylene. The polymers and copolymers which are to be treated, can contain up to about 25 percent of a fluorinated plasticizer. The fluorinated plasticizers are the lower members of the saturated perfiuorochloroolefin polymer series, for

example, polytrifiuorochloroethylene in the oil, grease and wax range. The addition of plasticizer to the polymer in some instances, advantageously modifies the characteristics of the polymer, for example, by increasing its pliability, etc. i

Admixing of the stabilizing agent with the polymer may be effected in a variety of ways although usually the standard mechanical techniques are preferred. The method to be employed in effecting the admixture is based on the particle size of the polymer and the stabilizing agent. Thus, if both the polymer and'stabilizing agent are in finely-divided form, conventional tumbling type mixers such as, a barrel mixer, conical mixer and mushroom mixer may be employed. If the polymer and stabilizing agent are not already finely-divided, then they must be ground in order to secure thorough admixture. Although the grinding of the stabilizing agent and of the polymer may be efiected separately, it is preferred that they be ground together since the presence of the stabilizing agent will also retard thermal degradation which is apt to result during the grinding operation. Grinding of the polymer and stabilizing agent may also be effected in conventional equipment such as ball and pebble mills, colloid mills and hammer mills. A particularly suitable piece of grinding equipment is the Mikropulvarizer, a hammer type mill which functions by forcing the material being ground through an appropriate sized screen by means of a hammer action.

For purposes of this invention, the polymer and stabilizing agent are considered as being finely-divided when about 100 percent passes through a #316: (0.223) sieve; Preferably, at least 95% passes through a #7 (0.11") sieve and still more preferably, at least 95% passes through a #12 (0.066") sieve. Admixing is more quickly effected and degradation of the polymer during the grinding operation prevented, when the stabilizing agent is in a more finely-divided form initially. Preferably, 100% of the stabilizing agent should pass through a #270 (0.0021") sieve, and still more preferably at least 98% through a #325 (0.0017") sieve. The sieve sizes given above are in the U. S. standard series, the number in parentheses is the sieve opening in inches.

the form of thin films which are more subject to high temperature effects. After grinding to the desired particle size, the stabilized polymer is then admixed with a suitable vehicle. Suitable vehicles are those which are generally known as lacquer thinners such as xylene, acetone, di-isobutyl ketone, etc. A particularly suitable vehicle is a mixture of xylene and di-isobutyl ketone. In applications where solvents are objectionable, aqueous-dispersions may be used. Usually, between about 10 and about of the stabilized polymer is added to the vehicle depending on the method of application of the dispersion. Generally, higher concentrations of polymer are used when a dispersion is to be applied by dip'or brush techniques, whereas spray techniques usually require a lower solids concentration.

Molding of the low or high density stabilized powder may be accompilshed by using suitable molding equipment at temperatures between about 415 F. and 625. F. and a pressure between about 500 and about 25,000 pounds per square inch. Detailed description of preferred molding processes may be found in U. S. Patent Nos. 2,617,149, 2,617,150, 2,617,151 and 2,617,152, issued November 11, 1952, to Louis C. Rubin. When used in the form of a dispersion, the polymer contained in a suitable vehicle such as a mixture of xylene and di-isobutyl ketone is applied by spray, brush or dip techniques, and is air-dried or heat-dried at a temperature up to about 302 F. after which it is fused at a temperature between about 464 F. and about 482 F. for a period of time between about one hour and about 24 hours, preferably about 12 hours to insure theproduction of a homogeneous film of high tensile strength. When the stabilized polymer of this invention is fabricated by any of the above described processes, a homogeneous polymer mass is produced which contains, intimately dispersed within its mass, the added stabilizing agent.

As indicated previously, when perfiuorochloroolefin polymers are maintained at elevated temperatures for In a preferred method of operation, between about 30 and about 70 percent of the finely-dividedv stabilizing agent is dry-blended with the polymer. The dry-blended powder is then put through a Mikropulvarizer fitted with between about an 0.02" and about a 0.2" screen preferably, with a 0.06" screen to insure thorough mixing. The stabilized concentrate is then dry-blended with an additional quantity of unstabilized polymer to reduce the concentration of stabilizing agent to the desired level. This finely-divided stabilized polymer powder, has a low apparent density and is suitable for use in certain types of molding operations, such as compression molding. In other types of molding operations, such as extrusion and injection molding, a high density molding powder is preferred. The low density molding powder is converted to a high density powder by passing it through an extruder and a multiplicity of rod dies. A rotating chopper in front of the die cuts the extruded rod into granules of a:desired size. To minimze polymer degradation during this operation, the temperature is maintained just high enough to compact the powder into granules without converting them completely into homogeneous pellets.

The low density molding powder may also be prepared for use in a dispersion. Conversion of the low density powder to a dispersion grade powder is efiected by grinding in a suitable mill, such as a ball mill, to reduce the particle size to the extent that about 98% will pass through a #270 sieve preferably through a #325 sieve. The higher concentration of stabilizing agent which is used with dispersion grade polymers serves to further retard degradation of the polymer during the prolonged grinding operation and also serves to retard degradation durng use since dispersion grade polymer is usually used in prolonged periods of time (for example during molding), the polymer chain is cracked, thereby reducing the molec: ular weight of the polymer. Since determination of molecular weights is a tedious process, an empirical test which tends to reflect the molecular weight of the sample under test, is used. In this test, the ZST value of the polymer is determined. Briefly, determination of the ZST value is carried out by molding a test strip 0.062" 0.003" thick, 2" long, and ii," wide. This strip is then notched at the center. The cross-section of the specimen at the notch is 0047:0001" wide by 00621-0003". The upper portion of the strip is held in position with a spring clip while a weighted spring clip totaling 7 /2 grams is attached to the other end of the specimen. The weighted specimen is then maintained at a temperature of about 300 C. in a suitable apparatus. The number of seconds required for the sample to break at the notch, is the ZST value. For evaluating the stabilizer of this invention, two ZST values were determined, namely the standard ZST value and the degradationZST value. The standard ZST value was determined by taking a sample of approximately 40 grams and molding it into a pellet approximately 2" in diameter and 5 in thick ness, by applying 12,000 p. s. i. pressure without heat. The pellet was then placed between two platens which were set to give a sheet 62 mils in thickness. The platens were then placed in a press, preheated for 3 minutes at about 260 C. without pressure and then heated at about 260 C. for an additional 3 minutes at 20,000 p. s. i. This pressed sheet was removed, cut into a notched strip, and its ZST value determined as described above. The time in seconds required to break the strip, at the notch, is the standard ZST value. The degradative ZST value was determined by preparing a pellet in the same manner as described for the standard ZST value determination, except that the pellet was preheated in a press at 300 C. for 5 minutes after which the specimen was heated at 300'. :C.:-under:a1pressure ;of:-abont.-20,000; pr-saiaforzan additionalsS minutes. .Thistsecdird strip was :cutiintoaa notched strip andzitsiZST valuetdeterminedaas described above. The. time in; seconds:frequired-sto:breakthis strip, at the notch,represents-.the:degradativeZSTWalue. qFor a fuller ,and more: complete understanding, oi' the "method and apparatus used in-determining values; reference rriay be ;had to application:SeriaLNo.4432 681,: filedrMay 27, 1954, by H. S. Kaufman and CtiRaGiannotta.

.1n:,order to illustrate thestabilizationreiiect of barium peroxide, a fnumberaoflsamples wereiprepared containing barium peroxidein different concentrations. together with various additives) lzlnapreparing these samples, .Mikropulvarized polymer was i admixednwiihxthe Ei'ndicated .additive by blending ina mortar and pestlerfortaboutiminutes. The mixtures were then molded .into: standard aand ;de-' gradative ZST;strips.: a j

"This example illustrates the stabiliiation dfahdmopolymer of trifluorochloroethylene having/a standard Z ST of about 427 'ln-prepari'rigl'the samples, theli'ndicated quantity of bariiim peroxide was added J to an amount oi polymer sufficient td 'b'ririgthe'tdtah sample weight up to 40. grams. The standard "and 'degradativeZST values r'e ported the table were dtermi'nedas described above.

7 Table 3 'ZST value ma mas; 3

Barlummeroxidepg; I

tive Standard Thisexampleillustrates the stabilizationrof av copolymer of trifluorochloroethylene .copolymerized, with about 5 molpercent of vinylidenefiuoride. Standard and degradativeZST valuesv were determined in the samemanner as describedwith-reference in the preceding example. The weightofbarium lpe roxide which .was added-to .an amountvof P lymer sufficient to bring the totalsample weight .upzto 40grams, .is indicatedin the table below.

Table .1

zsmveiue Barium peroxide, g. i l i 7 Standard Degradafive 421 17o 425, 302 408 .345 408 359 434, are

gThis example illustrates thestabilization' of azpigmented (olive-drab) homopolymer. of .trifiuorochloroe'thylene. The, homopolymer employed wasirom the samebatch as that used in determining the ZST values of Example I. The olive-drab pigmentidontainedIS npaTts of carbon, 25 parts of titanium dioxide, .24 -.parts ,.of .cadmium sulfide, parLof .zincf.sulfi l;e', and- 50 partscof rbarium sulfate. In preparing these samples, 0.2 gram of the olive-drab pigment and the quantity of barium peroxide indicated in the table were added to an amount of the polymer suflicient to bring the total sample weight up to 40,grams. By using combinations of cadmium sulfide, zinc sulfide, carbon, titanium dioxide, and barium sulfate in conjunction with barium peroxide, the polymer can be prepared in a variety of colors. Depending on the color required, at least one of the above described compounds is added to the stabilized polymer preferably in a concentration between about 0.1 and about 5 parts per 100 parts of vpolymer.

Table 2 V ZST value Barium peroxide, g.

' Standard Degradative EXAMPLE m This example illustrates the stabilization of a pigmented plasticized homopolymer of trifiuorochloroethylene. In this example, the polymer used was from the same batch as that reported in the preceding tables. The pigment employed was the same as that described j ..Table;4

ZST value Bariumperoxldegg. D d

i egra a- .Standard.

a tlve EXAMPLE V p This example presents data'illustratingtthe use ofsodiuin chlorateas an additive to polytrifluorochloroethylene.. -.In determining the Q Z ST values reported. below, the same procedure was employed as 'describedabove, using sodium chlorate as the additive. The'homopolymer of trifluorochloroethylene was from the same batch as that used in Example I. The quantity of sodium chlorate indicated in the table was added to an amount of polymer sufficient to bring the total sample weight up to 40 grams. Standard and degradative ZST test strips were then prepared and the ZST values determined as described above. These values are reported in the table below. From these values it Will be observed that some stabilizing effect is obtained. However, each of the samples was badly bubbled and the pressings were non-uniform. Consistent results were not obtained as evidenced by the tests in which 0.04 and 0.4 gram of sodium chlorate were added. In addition, the degradation products obtained with these additives were corro- ZST value Sodium chlorate, g.

Standard Degradatlve -Yar ious alterations and modifications of the-invention andfits aspects may become apparent'to thoseskilled in the art without departing from the scope of this invention; I Having thus described my-inv'ention, I claim: a 1. A novel plastic composition consisting of an admixture of a polymer of trifiuorochloroethylene selected from the group consisting of the homopolymer of trifluorochloroethylene and copolymers of trifluorochloroethylen'e'and vinylidene fluoride which contain not more than mol percent of vinylidene fluoride and between about 0.05 and about 20 parts of barium peroxide per 100 parts of said polymer, said polymer being inert to chemical cross-linking in the presence of barium peroxide. 2. A novel plastic composition for use as a molding powderconsistingof an admixture of a polymer of trifluorochloroethylene selected from the group consisting of the homopolymer of trifluorochloroethylene and copolymers of trifluorochloroethylene and vinylidene fluoride which contain not more than 5 mol percent of vinylidene fluoride and between about 0.1 and asoum parts of barium peroxide per 100 parts of said polymer, said polymer being inert to chemical cross-linking in the presence of barium peroxide.

3. A novel plastic composition for use in a dispersion consisting of an admixture of a polymer of trifluorochloroethylene selected from the group consisting of the homopolymer of trifluorochloroethylene and copolymers of trifluorochloroethylene and vinylidene fluoride which contain'not more than 5 mol percent of vinylidene fluoride and, between about 3 andabout 7 parts of barium peroxide per 100 parts of said polymer, said'polymer being inert to chemical cross-linking in the presence of barium peroxide.

4. A novel plastic composition consisting of an admixture of a plastic homopolymer of trifluorochloroethylene and between about 0.1 and about 3 parts of barium peroxide per 100 parts of said polymer, said polymer being inert to chemical cross-linking in the presence of bariumperoxide. 7 7 I 5. A novel plastic composition consisting of an admix ture of a copolymer of about 95 mol percent of trifluorochloroethylene and about 5 mol percent of vinylidene fluoride and between about 0.1 and about} parts of barium peroxide per 100 parts of said copolymer said copolymer being inert to chemical cross-linking in the presence of barium peroxide.

61' A novel plastic composition consisting of an admix' lure-of a polymer of trifluorochloroethylene and between about 0.1 and about-3 partsof barium peroxide per parts o'f saidpolym'er and between about 0.1 and about 5 pafts of at leas't one compound selected from the group consisting of carbon, titanium dioxide, cadmium sulfide, zinc sulfide, and barium sulfate per 100 parts of said polymerg'said polymer being inert to chemical cross-linking in the presence of barium peroxide.

7. A novel plastic composition prepared from a molding powder consisting of a homogeneous trifluorochloroethylene polymer mass selected from'the group consistingof the homopolymer of trifluorochloroethylene and copolymers of trifluorochloroethylene and vinylidene fluo ride which-contain not more than 5 mol percent of vinylidene fluoride and intimately dispersed therein between about 0.1 and about 3 parts of barium peroxide per 100 parts of said polymer, said polymer being inert to chemical cross-linking in the presence of barium peroxide;

8. A novel plastic composition prepared from a dispersion consisting of a homogeneous trifluorochloroethylene polymer mass selected from the group consisting of the homopolymer of trifluorochloroethylene and copolymers of trifluorochloroethylene and vinylidene fluoride which contain not more than 5 mol percent of vinylidene fluoride and intimately dispersed therein between about 3 and about 7 parts of barium peroxide per 100 parts of said polymer, said polymer being inert to chemical crosslinking in the presence of barium peroxide.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Zapp et al.: Journal of Polymer Science, vol. 9-10, pages 97 to 113, August 1942. (Copy in Division 60.) 

1. A NOVEL PLASTIC COMPOSITION CONSISTING OF AN ADMIXTURE OF A POLYMER OF TRIFLUOROCHLOROETHYLENE SELECTED FROM THE GROUP CONSISTING OF THE HOMOPOLYMER OF TRIFLUOROCHLOROETHYLENE AND COPOLYMERS OF TRIFLUOROCHLOROETHYLENE AND VINYLIDENE FLUORIDE WHICH CONTAIN NOT MORE THAN 5 MOL PERCENT OF VINYLIDENE FLUORIDE AND BETWEEN ABOUT 0.05 AND ABOUT 20 PARTS OF BARIUM PEROXIDE PER 100 PARTS OF SAID POLYMER, SAID POLYMER BEING INERT TO CHEMICAL CROSS-LINKING IN THE PRESENCE OF BARIUM PEROXIDE. 